Quaternary ammonium glyoxalidine derivatives of alpha-halogen carboxy acid esters of oxyalkylated phenol-aldehyde resins



Patented Jan. 8, 1952 QUATERNARY AMMONIUM GLYOXALHJINE DERIVATIVES OFALPHA-HALOGEN CAR- BOXY ACID ESTERS OF OXYALKYLATED PHENOL-ALDEHYDERESIN S Melvin De Groote, University City, and Bernhard Keiser, WebsterGroves, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Del.,a corporation of Delaware No Drawing. Application Decemberl3, 1948,Serial No. 65,087

8 Claims. (Cl. 260-53) The present invention is concerned with certainnew chemical products, compounds, or compositions which have usefulapplication in various arts. This invention is a continuationin-part ofour co-pending application Serial No. 726,208, filed February 3, 1947,and now abandoned. It includes methods or procedures for manufacturingsaid new chemical products, compounds, or compositions, as well as theproducts, compounds, or compositions themselves. Said new compounds orcompositions are quaternary ammonium compounds obtained by reactionbetween a hydroxylated glyoxalidine of the formula:

in which RC is the residue of the radical RCO, which, in turn, is theacyl radical of a detergentforming monocarboxy acid having at least 8and not more than 22 carbon atoms, and R is an alkylene oxide radicalhaving not over 4 carbon atoms and selected from the class consisting ofethylene oxide radicals, propylene oxide radicals, butylene oxideradicals, glycide radicals, and methylglycide radicals; and n is anumeral varying from 1 to 3; and the ester of an alphahalogenmonocarboxylic acid having not over 6 carbon atoms and hydrophilehydroxylated synthetic products; said hydrophile synthetic productsbeing oxyalkylation products of (A) an alpha-beta alkylene oxide havingnot more than 4 carbon atoms and selected from the class consisting ofethylene oxide, propylene oxide, butylene oxide, glycide, andmethylglycide; and (B) an oxyalkylation-susceptible, fusible, organicsolvent-soluble, water-insoluble, phenol-aldehyde resin; said resinbeing derived by reaction between a difunctional monohydric phenol andan aldehyde having not over 8 carbon atoms and reactive towards saidphenol; said resin being formed in the substantial absence of trifunc-'tional phenols; said phenol being of the formula:

in which R is a hydrocarbon radical having at least 4 and not more than12 carbon atoms and substituted in the 2,4,6 position; said oxyalkylatedresin being characterized by the introduction into the resin molecule ofa plurality of divalent radicals having the formula (R10)n, in which R1is a member selected from the class consisting of ethylene radicals,propylene radicals, butylene radicals, hydroxypropylene radicals, andhydroxybutylene radicals, and n is a numeral varying from 1 to 20; withthe proviso that at least 2 moles of alkylene oxide be introduced foreach phenolic nucleus.

Although the herein described products have a number of industrialapplications, they are of particular value for resolving petroleumemulsions of the water-in-oil. type, that are commonly referred to ascut oil, roily oil, emulsified oil, etc., and which comprisefinedroplets of naturally-occurring waters or brines dispersed in a moreorless permanent state throughout the oil which constitute thecontinuous phase of the emulsion. This specific application is describedand claimed in our co-pending ap lication'Serial No. 65,086, filedDecember 13, 1948, and now Patent 2,542,003, granted February 20, 1951.The new products are useful as wetting, detergent and leveling agents inthe laundry, textile and dyeing industries; as wetting agents andspreaders in the application of asphalt in road building'and the like;as a flotation reagent in the flotation separation ofvarious aqueoussuspensions containing negatively charged particles, suchas sewage,coal'washing waste water, and various trade wastes and the like; asgermicides, insecticides; emulsifying agents, as, for example,forcosmetics, spray oils, waterrepellent textile finishes; aslubricants, etc.

The esters of alpha-halogen monocarboxy acids with oxyalkylatedphenol-aldehyde resins which are converted to the quaternary ammoniumcompounds of the invention are described in 7 our Patent 2,542,003,granted February 20, 1951.

The phenol-aldehyde resins and their oxyalkylation are described in ourPatent 2,499,370, granted March '7, 1950. Reference is made to thesepatents for a description of the phenol aldehyde resins used, theiroxyalkylation and their conversion to alpha-halogen monocarboxy acidesters. For examples of phenol-aldehyde resins,

reference is made to Examples la through 103a of Patent 2,499,370. Forexamples of the oxyalkylated resins, reference is made to tables atcolumns 31 through 46 of Patent 2,542,003. For examples of thealpha-halogen monocarboxy acid esters of these oxyalkylated resins,reference is made to Examples 10 through 390 of Patent We have foundthat compounds which are particularly effective as demulsifying agentsand also advantageous for other uses, such as those previouslyenumerated, invariably are apt to be .those inwhich there are more thanthree ether linkages per .phenolrradical, and particularly.

3 those which have been oxyalkylated sufficiently to give a productwhich is water-miscible or water-soluble prior to'any subsequentreaction. In the hereto appended claims it will be noted that certain ofthe sub-generic claims are limited to the use of an initial reagent, towit, an oxyalkylated thermoplastic resin of the kind described, which isdistinctly hydrophile in character, at least to the extent that it iswatermiscible. One advantage of such reactant is that it can be combinedwith compounds such as bromostearic acid, followedby reaction withdimethyl octadecenylamine, or dimethyl octadecylamine and still yield afinal product havin very definite hydrophile properties, notwithstandingthe fact that the two subsequent reactants each have at least 18 carbonatoms. In any event, having obtained an oxyalkylated thermoplasticphenol-aldehyde resin 01 the kind described in either the non-hydrophiletype or the hydrophile type, preferably the latter, one reacts suchproduct with a suitable alpha-chloro fatty acid having not over 6 carbonatoms, or its equivalent, such as alpha-chloro acyl chloride, oranester, with the same limitation in regard to the carbon atom, If a lowmolal alpha-chloro fatiw acid is employed, then water is eliminated as aresultant of the reaction; whereas, if an alphachloro acyl chloride-is.employed, or a bromide is employed, then a halogen acid such ashydrochloric is eliminated. The amount of alphachloro fatty acidreactant may be suflicient to combine with all the stable reactivehydroxyl radicals present, based on the hydroxyl value,

or with only a fraction thereof; such as or 75%. One advantage in usinghydrophile oxyalkylated thermoplastic phenolaldehyde resins asreactants, is that one need not introduce as many quaternary ammoniumradicals as might otherwise be required to give distinct hydrophilecharacter, i. e;, the ability to form at least a permanent sol in water.

Having employed an alpha-chloro low molal fatty acid or its equivalent,the resultant product is a complete or fractional ester of suchalpha-chloro low molal acid, and the alphachloro atom is, of course,markedly reactive, The next step is to react such completeor fractionalester with an amino type compound of the kind exemplified by the priorformula:

N CH1} ll 011E330 H ncnlonzon A variety of such amines suitable forreaction will be described in the subject-matter immediately following.

The particular intermediate products supplying the amine reactant hereincontemplated are limited to types in which all amino nitrogen atoms aretertiary. Asa matter of convenience inthe manufacture, we prefer to usederivatives of ethylene diamine. Since ethylene diamine ordinarily comeson the market in the form of a 70% solution in water, and sinceaminoethyl ethanolamine (hydroxyethyl ethanoldiamine) is available in,substantially 100% concentration, we prefer to use this particularproduct as a raw material, insofar that it can be converted into the.glyoxalid-ine without destruction of the hydroxyl group-. This alsoapplies. to the derivatives; of ethylenediamine' and propylene oxide,butylene oxide, glycide, and methylglycide, for example,hydroxypropylene eth-ylenediamine, hydroxybutyl'i ethylenediamine, and.dihydroxypropyl ethylenediamine. Thus, one may obtain a homogeneouscompound. such as l-hydroxypropyl-Z-heptadecenyl glyoxalidine,l-hydroxybutyl-Z-heptadecenyl glyoxalidine,l-dihydroxybutyl-Z-heptadecenyl glyoxalidine, etc.

Similarly, where the heptadecenyl radical appears resulting from the useof oleic acid as a raw material, one can use stearic acid, naphthenicacid, oranyone of a number of detergentforming monocarboxy acids-havingat least 8 and not more than 22 carbon atoms. Thus, other examplesinclude l-hydroxyethyl-2-heptadecyl glyoxalidine,l-hydroxybutyl-2-heptadecylglyoxalidine, 1-dihydroxybutyl-2-heptadecylglyoxalidine, etc.

An alternate procedure is to produce the imidazoline and react theimidazoline with one to six moles of a suitable oxyalkylatin agent, aspreviously described. Ourv preference is to react the imidazoline with asingle mole of the oxyalkylating agent. In this connection, as to themanufacture of undecylimidazoline, heptadecylimidazoline,heptadecenylimidazoline, and-other suitable imidazolines, see U. S.Patent No. 2,215,- 862, dated September 24, 1940, to Waldmann. Havingobtained such imidazoline, it need only be subjected to treatment withethylene oxide, etc., in the customary manner. This particularprocedure, oxyalkylation, is described in detail in the patentliterature, including U. S. Patent No. 2,353,708, dated July 18, 1944,to De Groote and Keiser, Attention is directed to the fact that thispatent also describes the manufacture of imidazolines by reference tovarious patents which include ethylenediamine as a reactant. In essence,then, the amine reactants are best described in the following formula:

' in which the characters have their previous significance and nrepresents the numerals l to 6.

Referring to a consideration of the alphachloro fatty acids or thechlorides. it is our pref erence to use chloroacetic acid, for thereason that it is cheap and particularly reactive. Chloroacetyl chlorideis a preferred reactant, from the standpoint of reactivity. but isobjectionable for two reasons-one being that eliminating hydrochloricacid in the reaction, there is a tendency to cause corrosion of theapparatus, unless especially designed, and secondly, this reactant iscomparatively expensive. However, except for these two objections, itmay be considered as a preferred reactant. Our preference. is to use.any alpha-halogen carboxylic acid, if not over six carbon atoms. Othersuitable acids include alpha-chloropropionic acid, alpha chlorobutyricacid, alpha bromoisocaproic acid, bromoacetic acid, iodoacetic acid,etc. The acyl halides or anhydrides of these acids, of course, may beemployed. In many instances the alpha-halogenated acyl chloride is asreadily available as the alpha-halogen acid. The reason for this is thefact that it is difficult to halogenate an acid so as to introduce thehalogen in an alpha position, but an acyl halide reacts more rapidly andthe halogen enters the alpha position, due to the negative effect ofboth the chlorine atom and the carbonyl atom. Under such circumstances,where the alpha-chloroacyl acid is available, there is no reason, ofcourse, to hydrolyze an acyl chloride to the acid in order to use theacid instead.

Specific examples of glyoxalidine or imidazoline which can be reactedwith ethylene oxide or propylene oxide for the reason that they have alabile hydrogen (a hydrogen atom directly attached to an oxygen atom ora nitrogen atom, or both) may be illustrated by the following examples:

' /NCH2 CuHnC N- H: l

2-undecylimidazoline N-CH2 i1Ha5.C

N- H, H

2-heptadecylimidazoline NCH: sHmC I NlHa 2H OH2-0etyl,il-hydroxyethylimid azoline N-CH:

uHas- N H: t

2-oleylimidazoline N-CH,

G H .O

2H4.NH2 2-phenyl,l-aminoethylimidazollne %N H2 14H27.C

2-substituted imidazoline from naphthenic acid (from kerosene) andtriethylenetetramine N- H: n as- 0 C 2H4.NH: Z-heptadecyl,l-aminoethylimidazoline 2H4.NH.C2H4.NH, Z-heptadecyl,1-diethylenediaminoimidazoline.

' glycide and then converting into the amide with Referring to thereaction of chloroacetic acid with an oxyalkylated resin, this may beillustrated by considering a structural unit of the resin as a unit.Thus, a structural unit may be depicted in the following manner:

After reaction with chloroacetic acid, the structural unit appears asfollows:

H RE

The thermoplastic resins employed as raw materials are hard, brittleresins, varying in color from a pale pink to a dark amber. Theoxyalkylated resins derived from the thermoplastic resins vary fromresinous to subresinous materials to thick oils or wax-like bodies. Thecolor, as a result of the next reaction, formation of the chloroacetate,is apt to be much darker in appearance, varying from honey color to adeep brown or amber. Such oily 0r sub-resinous materials are thenreacted with amines of the kind described, by simply heating toapproximately C. to C. for approximately 2 to 8 hours. Often thereaction is complete within as little as a half an hour, and may becomplete at an even lower temperature than the one suggested. Thereaction involved, ignoring side reaction, may be illustrated asfollows:

HH l

As will be pointed out subsequently, the acylated tertiary amine mayhave two or more basic amino nitrogen atoms and two or more acylradicals. In other words, such polyamine would be polyfunctional towardsthe halogenated acid ester, and thus, could combine with more than onemole of halogenated acid ester. t

It will be noted :that the hydroxylated glyoxalidine has two basictertiary nitrogen atom. For this reason no effort is made to indicatewith which particular nitrogen atom combination takes place. Likewise,it is obvious that, 2 moles of the halogenated acid ester could combinewith 1 mole of the glyoxalidine. Previous reference has been made to theglycxalidines employed as reactants. Such reactants are obtained, aspreviously indicated, by combining ethylene diamine with a moleof analkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide,glycide, or methyl a mole of a detergent-forming monocarboxy acid Y orits equivalent.

It is well known that certain monocarboxy organic acids containing l3carbon atoms or more,

and not more than: 32 carbon atoms; are characterized by thefact thatthey combine with alkalis to produce? soap or soap-like materials; Thesedetergent-forming acids include fatty acids, resin acids,petroleumacids, etc. For. the sake of convenience, these acids will beindicated by the formula R.COOH. Certain derivatives of detergentformingacids react with alkali to produce soap or soap-like materials, and arethe obvious equivalent of the unchanged orunmodified detergentformingacids. For instance, instead of fatty acids, one might employ thechlorinated fatty acids. Instead of theresin acids, onemight employ thehydrogenated resin acids. Instead of naphthenic acids, one might employbrominated naphthenic acids, etc.

The fatty acids are of the type commonly referred to as higher fattyacids; and of course, this is also' truein regard to derivatives ofthe-kind indicated, insofar that such derivatives are ob:- tained' fromhigher fatty acids. acids include not only naturally-occurringnaphthenic acids, but-also acids obtained by the oxidation of wax,parafiin, etc. Such acids may have For instance, see U. S. Patent No.2,242,837, dated. May 20,1941, to

as-many as 32 carbon atoms.

Shields.

The hydroxy-lated glyoxalidine used as a react'ant is preferably derivedfrom: unsaturated fatty acids having 18- carbon atoms. Such unsaturated'fatty acids include oleic' acid, ricinoieic acid, linoleic acid,linolenic acid, etc. One may employ mixed fatty acids, as, forexample',. the

fatty acids obtained from hydrolysis of cottonseed oil; soyabean oil,etc; More specifically, our ultimate preference is to use a glyoxalidineobtained from unsaturated fatty acids, and more especially, unsaturatedfatty acids containing a hydroxyl radical, or unsaturated fattyacidswhich have been subjected to oxidation. In-addition to syntheticcarboxy acids obtained by theoxidation of paraffins or the like, thereis the somewhat analogous class obtained by treating carbon dioxide orcarbon monoxide, in the presence of hydrogen or an olefine, with steam,or by causing a halogenated hydrocarbon to react With-potassium cyanideand saponifying the product obtained. Such:products or mixtures thereof,having at least and not more than 32 carbon atoms and having at leastone carboxyl group or the equivalent 1 thereof, are suitable asdetergent-forming monocarboxy acids; and another analogous class equallysuitable, is the mixture of carboxylic acids obtained by the alkalitreatment of alcohols of high molecular weight formed in the catalytichydrogenation of carbonmonoxide.

As is well known, one need not use a high molal carboxy acid, such as afatty acid, for introduction of the acyl group or acyloxy group; Anysuitable functional equivalent such as the acyl.

halide, the anhydride, ester, amide, etc., may be employed.

Thus, after a detergent-forming monocarboxy acid and preferably onehaving 8 to 18" carbon atoms, is reacted with the hydroxylated ethylenediamine to form the amide, a subsequent reaction is employed, to wit,conversion of the amide into the glyoxalidine.

The manufacturin procedure can also be reversed by forming the amide ofthe ethylene diamine, converting into a glyoxalidine having a secondarynitrogen atom, thus:

NCH:

CITE-(336' Such glyoxalidine can. then beoxyalkylated; imae N CH2 Riddin G 10) nH R10 is the radical obtained: by deox-ygenation of the acylradical RCO of a detergent-forming monocarboxy acid having at least 8and not more. than 32' carbon atoms, and preferably, not over 22 carbonatoms; RrOis an alkylene oxide radical f having not over 4 carbon atomsand selected from the class consisting of ethylene oxide, propylene.oxide; butylene oxide, glycide and methyl glycide, audit" is a numeralvarying from 1 to3. Having obtained both the halogenated acid ester;such as l a chloroacetic acid ester of the kind previously described andthe hydroxylated glyoxalidine, all that is required. is to react theproducts so as to form a quaternary ammonium compound, all of which maybe illustrated by the following examples:

Such imidazoline was then treated with ethylene oxide in the molarratiosof 1 to 1 3 to 1 and 5 to 1, being on the-basis of oxide to imidazoline.Such derivatives were then employed in preparation of the followingexamples of quaternary ammonium derivatives:

Example 1 400 grams of the xylene-containing ester reactant identifiedas of Patent 2,542,003, were mixed with an equimolar amount, or 144grams of oxyethylated imidazoline (3 moles of ethylene oxide to one moleof the imidazoline) described in the text immediately preceding. Thisimidazoline was obtained from" tetra'ethylenepentamine and stearicacid-.. To the mixture there was added an amount on xylene equivalent toabout one-fourth the weight of tertiary amine. In the instant case-theamount added was 35 grams.

Although inthe instant experimentand those subsequently noted, the;solvent employed was xylene, one may employ oymene or decalin. Thereaction takes place at comparatively low temperature, as previouslysuggested, and, in any event, under 215 0., and? frequently as low as C.A convenient temperature of reaction is to C. Thus, if xylene isemployed, as is our preference, and if there is present at least 25% byweight of the combined reactants in the form of xylene, there i theautomaticv effect in regard to the temperature, and, the xylene may bepermitted to remain after the reaction is complete. If desired, it maybe eliminated in any convenient manner, such: as distillation or vacuumdistilla tion. all cases we have used a time periodbf 2 to 4 hours andfound the reaction was'complete at'the end of the 4 hour period. Insomecases we believe the reaction was complete in 30 to 45 minutes. In thisparticular reaction, and in most of the subsequent reactions, we haveattempted to have suflicient xylene present, adding more if need be, sothe final reaction product contains approximately 40% xylene and- 60%quaternary compound. A solution of this concentration-is usually freefrom any highly viscous or tacky properties, and is convenient for usein a pump, which is particularly desirable when used as a demulsifier. I

The final product obtained was a viscous, deep amber colored fluid,completely water-soluble, and

containing 38.2 xylene.

Eai ample 2d The same procedure wa 'followed as in Example 1d, exceptthat 400 grams of ester identified as 20 of Patent 2,542,003 werereacted with 175 grams of the oxyethylated imidazoline described inExample ld, preceding. The final product was a viscous, deepamber-colored liquid, completely water-soluble and containing 41%xylene.

Example 3d liquid, containing 37.4 xylene.

' Example 511 The same procedure was followed as inExarnple 1d, exceptthat 400 grams of ester identified as 30 of Patent 2,542,003 werereacted with 123grams of the oxyethylated imidazoline described inExample lcl, preceding. The final product was a viscous, deepamber-colored, water-soluble liquid, containing 37.6% xylene.

Example 6d 1 The same procedure was followed as in Example 1d, exceptthat 400 grams of ester identified as 230 of Patent 2,542,003 werereacted with 168 grams of the oxyethylated'imidazoline described inExample 1d, preceding. The final product was a viscous, deepamber-colored, water-soluble liquid, containing 33.6% xylene.

Example 7d .The same procedure was followed as in Example 1d, exceptthat 400 grams of the ester reactant identified as 240 of Patent2,542,003 were reacted with 118 grams of the oxyethylated imidazolinepreviously described as being obtained by use of one mole of ethyleneoxide per mole of imidazoline instead of the 3 to 1 ratio reactantemployed "in the previous six examples. The imidazoline itself, was, aspreviously stated, obtained from stearic acid andtetraethylenep'entarnine. The product obtained was a. viscous,-deepambercolored liquid which gave a cloudy solution in water and contained35 xylene.

Emample 8d The same procedure was followed 'aS-lli Example 1d,preceding, except that 400 grams of the ester reactant identified as ofPatent 2,542,003 were reacted with 163 grams 'of the oxyethylatedimidazoline obtained by use of 5 moles of ethylene oxide per mole ofimidazoline. This derivative has been described previously and wasobtained from the imidazoline which was obtained by reaction betweenstearic acid and tetraethylene pentamine. The product obtained was aviscous, deep amber-colored, water-soluble liquid, containing 37%xylene.

Example 9d The same procedure was followed as in EX- ample 1d,preceding, except that 400 grams of the ester derivative identified as20 of Patent 2,542,003 were reacted with 197 grams of the 5 to 1 ratiooxyethylated imidazoline described in Example 8d, preceding. The productobtained was a viscous, deep amber-colored, water-soluble liquid,containing 39.6% xylene.

Emample 10d The same procedure was followed as in'Example 1d, preceding,except that 400 gramsof the ester derivative identified as of Patent2,542,003 were reacted with 184 grams of the 5 to 1 ratio oxyethylatedimidazoline described in Example 8d, preceding. The product obtained wasa viscous, deep amber-colored, water-soluble liquid, containing 43%xylene.

Example 11d The same procedure was followed as in Example lcl,preceding, except that 400 grams of the ester derivative identified asof Patent 2,542,003 were reacted with 164 grams of the 5 to 1 ratiooxyethylated imidazoline described in Example 811, preceding. Theproduct obtained was a viscous, deep amber-colored, very watersolubleliquid, containing 36% xylene.

Example 12:1

The same procedure-was followed as in Example 1d, preceding, except that400 gramsof the ester derivative identified as 30 of Patent 2,542,003were reacted with 131 grams of the 5-to-1 ratio oxyethylated imidazolinedescribed in Example 811, preceding. The product obtained was a viscous,deep amber-co10red, verywatersoluble liquid, containing 35.8% xylene.

Example 13d The same procedure was followed as in Example 1d, preceding,except that 400 grams of the ester derivative identified as 230 ofPatent 2,542,003 were reacted with 189 grams of the 5-to-l ratiooxyethylated imidazoline described inExample 8d, preceding.- The productobtained was a viscous, deep amber-colored, yery, water,- solubleliquid, containing 32.6% xylene.

Example 14d The same procedure was followed as in Example ld, preceding,except that 400 grams of the ester derivative identified as 24c ofPatent 2,542,003 were reacted'with'l58 gramsof the 5-to-1 ratiooxyethylated imidazoline' described in Example'8d,preceding. The productobtained was aviscous, deep "amber-colored, very watere soluble liquid,containing 33% xylene. 9

2,581, 3&6

oxalidine of the formula:

in which RC is :the residue of the radical RCO, which, in turn, istneacyl radical of a detergentforming monocarboxy acid having at least 8and not more than 22 carbon atoms, and R is an alkylene oxide radicalhaving not over "4x03113011 atoms and selected from the class consistingof ethylene oxide radicals, propylene oxide radicals,

'butylene oxide radicals, glycide radicals, and 'methylglycide radicals;and-n' is a-numeral'varyingfrom 1 to 3; and an ester in which the acylradical is that of an -alpha-halogen monocarboxylic acid having not over'6 carbon atoms and composed of carbon, hydrogen, oxygen and halogen andthe alcoholic radical is that of certain hydrophile polyhydric syntheticproducts; "said hydrophile synthetic products being o y y tion productsof (A) an alpha-beta allgylene oxide having not more than 4 carbon atomsandselected from the class consisting of ethylene oxide, prqpyleneoxide, 1butylene oxide, glycide, and methylg'lycide; and ('B) anoxyalkylation-susceptible, fusible, organic solvent-soluble,water-insoluble, phenol-aldehyde resin; said resin being derived'byreactionrbet ween adifunctional monohydric phenol and an aldehyde havingnot over 8 carbon atoms and having one functional group reactive towardssaid phenol; said resin being formed in the substantial absence ofphenols of functionality greater than two; said phenol .being of theformula:

in which R is a hydrocarbon radical having at least 4andnot more than 12carbon atoms and substituted in one of the positions ortho and para;said oxyalkylated resin being-characterized by the introduction into theresin molecule at the phenolic hydroxyls 'of a pluralityof divalentradicals having the formula (R10)-n, in which R1 is a member selectedfrom theclass-consisting of ethylene radicals, propylene radicals,butylene radicals, hydroxypropylene radicals, and hydroxybutyleneradicals, and -n is a humeral varying from 1 to with the proviso thatatleast 2 moles of alkyleneoxide be introduced for each phenolic nucleus.7

*2. A quaternary ammonium compound obtained by reaction "between ahydroxylated glyoxalidine of the formula:

in'which RC is the residue of the radical RCO, which, in turn, isthe-acyl radical of a-detergentforming monocarboxy acid having at least-,8 and nottmore-more than 22 carbon atoms, and R10 is an alkylene oxideradical having mot over 4 carbonatoms and selected irom the ,classconsisting ofethylene oxideradicals,propylene-oxide radicals, butyleneoxide radicals, I glycide radicals, andmethylglycide radicals; and n isanumeral varying from 1 to 3; andca chloroacetateof certain hydrophilesynthetic products; saidhydro- 'phile synthetic products being,oxyalkylation products of (A) an alpha-beta alkylene oxide having notmore than 4 carbon atoms andselected from the class consisting ofethylene oxide, propylene oxide, butylene oxide, .glycide andmethylglycide; and (B) an oxyalkylationesusceptible, fusible,organicsolvent-soluble, waterinsoluble, phenolaldehyde resin; said,resin being derivedby reaction between adifunctional monohydric phenoland an aldehyde having .not over 8 carbon atoms and havingrvonefunctional group reactive towards said phenol; said resin being formedin the substantial absence of phenols of functionalitygreater than two;said phenol being of the formula:

in which R, is a hydrocarbon radical having at leastd and not more than12 carbon atoms .and substituted in one ,of the positions ortho andpara; said oxyalkylated resin being characterized by theintroductioninto the resin moleculeat the phenolic hydroxyls of aplurality of divalent radicals having thecformula (R10) n, in which R1is a member selected from theclass consisting of ethylene radicals,propylene radicals, butylene radicals, hydroxypropylene radicals, andhydroxybutylene radicals, and n is a numeral varying from 1 to 20; withproviso that at least'2 moles of .alkylene oxide be'introduced for eachphenolic nucleus; and with the final proviso that the hydrophileproperties of the ultimate quaternary ammonium compound as well as theoxyalkylated resin in an equal weight of xylene are sufficient toproduce an emulsion when said xylene solution is shaken vigorously withone to three volumes of water.

3. A quaternary ammonium compound 0b- 4 tained by reaction betweenahydroxylated glyoxalidine of the formula:

IN--'CH2 lin Hn (R 0) ME in which RC is the residue of the radical RCO,which, in :turn,-is'the acyl radicalof a detergentformingmonocarboxyacidhaving at least 8 and not more than '22 carbon atoms, and R10 is analkylene-oxide radical having not over 4 carbon atoms 'andselected fromthe class consisting of ethyleneoxide radicals, propylene oxideradicals, butylene oxide radicals, glycide radicals, and methylglycideradicals; and n is a numeral varying from 1 to 3; and a chloroacetate ofcertain 'hydrophile .polyhydric synthetic products; .said hydrophilesynthetic products being oxyethylation products of (A) ethylene oxide,and '(B) an oxyethylation-susceptible, fusible, organic solvent-soluble,water-insoluble phenolaldehyde resin; said resin being derived byreaction between a-difunctional monohydric phenol andan aldehyde havingnot over 8 carbon atoms and'having one functional group reactive'towardssaid phenol; said resin being formed in the substantial absence :ofphenols of functionality in which R is a hydrocarbon radical having atleast 4 and not more than 2 carbon atoms and substituted in one of thepositions ortho and para; said oxyethylated resin being characterized bythe introduction into the resin molecule at the phenolic hydroxyls of aplurality of divalent radicals having the formula (021140)"; wherein nis a numeral varying from 1 to 20; with the proviso that at least 2moles of ethylene oxide be introduced for each phenolic nucleus; andwith the final proviso that the hydrophile properties of the ultimatequaternary ammonium compound as well as the oxyethylated resin in anequal weight of xylene are suflicient to produce an emulsion when saidxylene solution is shaken vigorously with one to three volumes of water.

4.. A quaternary ammomium compound obtained by reaction between ahydroxylated glyoxalidine of the formula:

N(R1O)'H in which RC is the residue of the radical RCO, which, in turn,is the acyl radical of a detergentforming monocarboxy acid having atleast 8 and not more than 22 carbon atoms, and R10 is an alkylene oxideradical having not over 4 carbon atoms and selected from the classconsisting of ethylene oxide radicals, propylene oxide radicals,butylene oxide radicals, glycide radicals, and methylglycide radicals;and n as a numeral varying from 1 to 3; and a chloroacetate of certainhydrophile synthetic products; said hydrophile synthetic products beingoxyethylation products of (A) ethylene oxide, and (B) anoxyethylation-susceptible, fusible, organic solventsoluble,water-insoluble, low-stage phenol-aldehyde resin having an averagemolecular weight Number corresponding to at least 3 and not over '7phenolic nuclei per resin molecule; said resin being derived by reactionbetween a difunctional monohydric phenol and formaldehyde; said resinbeing formed in the substantial absence of phenols of functionalitygreater than two; said phenol being of the formula:

in which R is an aliphatic hydrocarbon radical having at least 4 and notmore than 12 carbon atoms and substituted in one of the positions orthoand para; said oxyethylated resin being characterized by theintroduction intothe resin molecule at the phenolic hydroxyls of aplurality of divalent radicals having the formula (Cal-M; wherein n is anumeral varying from 1 to 20; with the proviso that at least 2 moles ofethylene oxide be introduced for each phenolic nucleus; and with thefinal proviso that the hydrophile properties of the ultimate quaternaryammonium compound as well as the oxyethylated resin in an equal weightof xylene are sufficient to produce an emulsion when said xylenesolution is shaken vigorously with one to three volumes of water.

5. The product of claim 4, wherein R is substituted in the paraposition.

6. The product of claim 4, wherein R is a butyl radical substituted inthe para position.

7. The product of claim 4, wherein R. is an amyl radical substituted inthe para position. 8. The product of claim 4, wherein R is a nonylradical substituted in the para position.

MELVIN DE GROUTE. BERNHARD KEISER.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Name Date 2,499,365 De Groote Mar. '7, 1950

1. A QUATERNARY AMMONIUM COMPOUND OBTAINED BY REACTION BETWEEN AHYDROXYLATED GLYOXALIDINE OF THE FORMULA: